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WO2018118951A1 - Couches protectrices pour batteries à électrodes métalliques - Google Patents

Couches protectrices pour batteries à électrodes métalliques Download PDF

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Publication number
WO2018118951A1
WO2018118951A1 PCT/US2017/067357 US2017067357W WO2018118951A1 WO 2018118951 A1 WO2018118951 A1 WO 2018118951A1 US 2017067357 W US2017067357 W US 2017067357W WO 2018118951 A1 WO2018118951 A1 WO 2018118951A1
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electrolyte
anode
ionic
rechargeable battery
metal anode
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Inventor
Lynden A. Archer
Zhengyuan TU
Snehashis CHOUDHURY
Shuya WEI
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Cornell University
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Cornell University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • DMR-1609125 and DMR-1120296 awarded by the National Science Foundation and grant numbers DE-AR0000750 and DE-FOA-001002-2265 awarded by the Department of Energy. The government has certain rights in the invention.
  • the present disclosure relates to protective layers for metal electrode batteries, methods of making the protective layers, and batteries comprising the protective layers.
  • High energy rechargeable batteries based on active metal Li, Na, Al, Si,
  • Sn, Zn, etc. anodes are among the most important electrochemical energy storage devices to supply power for rapidly evolving technologies, including the fields of portable electronics, advanced robotics, electrification of transportation, etc. It has long been understood that such metal based anodes offer factors of 2-10 times higher specific capacity (e.g., 3860 mAh/g for Li), compared with the carbonaceous anode (360 niAh/g) used in lithium ion battery technology. Some metal anode batteries are also advantageous because they enable the development of high-energy unlithiated materials, such as sulfur, oxygen, and carbon dioxide as the active species in the cathode. This raises the prospect of multiple battery platforms that offer large improvements in specific energy on either a volumetric or mass basis.
  • Ge are able to reversibly form alloys with lithium (e.g., Li 44 Sn), meaning these materials provide certain capacity in rechargeable lithium metal batteries.
  • lithium e.g., Li 44 Sn
  • Si, Sn, In, Mg, and Ge undergo large volume changes (as high as 300%) upon lithiation, which destroys electrical connection with the current collectors and causes premature battery failure. The effects are even more severe for batteries based on sodium.
  • This problem was previously addressed by two methods: creating composite anodes in which the metal is integrated with an inert metal of conductive carbon (e.g. graphene, graphite, carbon black, carbon nanotubes), or by fabricating the active materials (e.g.
  • Si, Sn, In, Mg, Ge Si, Sn, In, Mg, Ge
  • the first method inevitably lowers the specific capacity as the inert metal or carbon materials used in the composites only serve as mechanical reinforcement for the active Si, Sn, In, Mg or Ge material and does not participate in the electrochemical reaction. Additionally, the alloying process is typically slow, and ideally requires higher temperature than those normally used in batteries for long-term stability. Fabricating the active material in the form of nanostructures does extend the anode lifetime, but comes at considerable costs in terms of the lower density of the active material, which reduces the specific energy on a volume basis of the electrode. The added costs of the processes required to create nanostructures in the desired shapes at scale and with high degrees of reproducibility for battery manufacturing also introduce new challenges that have so far proven to be stubborn roadblocks to commercialization of batteries employing metals as anodes.
  • An advantage of the present disclosure is a battery having a protected metal electrode, e.g., metal anodes that comprise substantially metallic lithium, metallic sodium, metallic aluminum, metallic zinc, etc.
  • the battery is a rechargeable battery that can include a metal anode, a cathode and an electrolyte, in which the metal anode has an ionic membrane thereon.
  • the ionic membrane can continuously supply ions near the anode electrode by providing a halogenated salt at or near the anode-electrode interphase, for example. The ionic membrane can further protect the metal anode.
  • a rechargeable battery comprising a metal anode, a cathode and an electrolyte, wherein the metal anode has an ionic membrane thereon.
  • the ionic membrane can be formed from ionomers including polymerizable ionic liquid monomers to form an ionic polymer membrane or from halogenated alkyl anion salts to form alkyl anions tethered to the metal anode.
  • the ionic membrane can include an ionic polymer membrane directly on the metallic anode, e.g., a metallic sodium anode.
  • ionic polymer membranes can be formed from one or more polymerizable ionomers, such as one or more polymerizable ionic liquids (IL) having one or more allyl or vinyl groups and having an anion.
  • the polymerizable ionomers can be included with an electrolyte of a rechargeable battery.
  • the ionic membrane can include alkyl anions tethered to the metal anode, e.g., a metallic lithium anode.
  • the metal anode e.g., a metallic lithium anode.
  • Such ionic membranes can be formed from ionomers of halogenated alkyl anion salts, such as one or more halogenated alkyl sulfonate salts.
  • the halogenated alkyl anion salts can be included with an electrolyte of a rechargeable battery.
  • the anodes protected with the ionic membrane of the present can be cycled stably with high Coulombic efficiency at high current densities.
  • metal anodes protected with ionic membranes of the present disclosure can exhibit coulombic efficiency exceeding 90% such as exceeding 95%.
  • Such protected anodes can exhibit stable cycling of over 100 cycles such as over 150 cycles.
  • Other aspects of the present disclosure include processes for preparing ionic membranes on metallic anode electrodes, which can be used in a rechargeable battery. Such processes include electropolymerizing a polymerizable ionic liquid monomer onto the metal anode to form an ionic membrane thereon. Other processes include adsorbing halogenated alkyl anion salts onto a surface of the metal anode electrode to form an ionic membrane thereon. The IL monomer and the halogenated alkyl anion salts can be included with an electrolyte of the rechargeable battery. The addition of such ionomers in the electrolyte can help in the regeneration of the ionic membrane in repeated cycling of the battery.
  • Figure 1 is a schematic representation of forming an ionic polymer membrane on a surface of a metal anode, e.g., a sodium anode, in accordance with an embodiment of the present disclosure.
  • a metal anode e.g., a sodium anode
  • Figure 2 is a plot showing cell failure time at various current densities derived from constant current polarization test of Na/Na symmetric cell with and without 20 wt% DAIM in the electrolyte.
  • Figure 3A shows cycling performance of Na 3 V 2 (P0 4 )3 cells with and without protected sodium metal anode at 100 mA/g of the active material in the cathode.
  • Figure 4 is a schematic representation of forming an ionic membrane on a surface of a metal anode, e.g., a lithium anode, in accordance with an embodiment of the present disclosure.
  • a metal anode e.g., a lithium anode
  • Figure 5 is a plot comparing interfacial and bulk impedance values for ionomer-based and control electrolytes as a function of time.
  • the circles denote results with the control electrolyte (1 M L1NO 3 - N,N-dimethylacetamide (DMA)), whereas the squares and triangles represent batteries with 10 and 5% (by weight) ionomer additive, respectively, with the same electrolyte (open symbols represent bulk impedance and solid symbols represent interfacial impedance).
  • DMA N,N-dimethylacetamide
  • Figure 6 is a voltage profile of the LilISS cell plotted over time.
  • Li + ions were deposited onto the stainless steel side at a current density of 1 niA/cm 2 for 10 hours, after which the cell was kept at rest for an additional 10 hours, as shown in the current-versus-time curve.
  • the red line represents the profile of the control electrolyte (1 M L1NO 3 -DMA), whereas the black line is for the same electrolyte enriched with 10% (by weight) ionomer additive.
  • the dashed line in the current-versus-time graph is the applied current for both cases.
  • Figure 7 is a plot of cycle number associated with divergence of voltage against respective current densities for a LilISS cell in which lithium with 10-mAh/cm2 capacity is deposited onto SS, and the battery was charged and discharged consecutively at various current densities.
  • Figure 8 shows end voltage of charging cycle for the control and the ionomer- added electrolyte plotted as function of cycle number.
  • Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.
  • the present disclosure provides protective layers for electrodes (e.g., anodes) of batteries.
  • the present disclosure also provides methods of making protective layers for the electrodes of batteries, and devices comprising same.
  • Various embodiments and examples describe proving safe, stable, air-insensitive metal anodes (e.g., lithium or sodium metal anode) by protecting the surface with an ionic membrane layer through in situ or ex situ facile wet chemistry reaction, with no harmful byproducts generated.
  • the ionic membrane provides desirable (e.g., low) surface impedance and protects metallic anodes from parasitic reaction with the electrolyte.
  • the methods disclosed herein can be readily incorporated into large- scale manufacturing.
  • a metallic anode is protected by an ionic membrane directly on a surface of the anode exposed to electrolyte.
  • the protected anode can be part of a rechargeable battery including the metal anode, a cathode and an electrolyte.
  • the ionic membranes of the present disclosure can be formed from ionomers.
  • an ionomer is a compound that has ionizable or ionic groups, or both and that can either polymerize to form an ionic membrane on a surface of a metallic anode or can adsorb on the surface of the metallic anode to form an ionic membrane thereon.
  • the ionomers form thin conformal coatings directly on the anode surface exposed to the electrolyte.
  • Ionic membranes prepared from ionomers of the present disclosure can continuously supply ions near the anode electrode and stabilize anode metal.
  • the ionic membrane can have a thickness in the range of a monolayer to micron scale, e.g., from about 5 nm to about 500 microns.
  • the ionic membrane can include an ionic polymer membrane directly on the metallic anode.
  • Such ionic polymer membranes can be formed from polymerizable ionomers, which can be included with an electrolyte of a rechargeable battery.
  • Useful polymerizable ionomers of the present disclosure include, for example, polymerizable ionic liquids (IL) having one or more allyl or vinyl groups and a corresponding anion.
  • Such IL monomers include 1,3-diallyl imidazolium perchlorate (DAIM), l-allyl-3-vinyl imidazolium perchlorate (AVIM), 1,3-diallyl piperidinium hexafluorophosphate, 1,3-diallyl piperidinium bis(trifluoroethanesulfonyl)imide, 1,3-diallyl imidazolium bis(fluorosulfonyl)imide, etc.
  • the IL monomer has more than one polymerizable group and a corresponding anion.
  • the ionic membrane can include alkyl anions tethered to the metal anode.
  • Such ionic membranes can be formed from ionomers of halogenated alkyl anion salts, e.g., halogenated alkyl sulfonate salt, which can be included with an electrolyte of a rechargeable battery.
  • halogenated alkyl anion salts of the present disclosure include, for example, those with the following formula:
  • X represents a halogen such as a chlorine, bromine, iodine
  • alkyl represents a Ci_i 2 , e.g., C2-6 divalent alkyl group
  • A represents a anion salt such as a sulfonate metal ion salt, e.g., lithium sulfonate, where the metal ion is preferably a metal ion corresponding to the metal of the anode.
  • Examples of ionomers that can absorb onto a metal anode include 2-bromoethanesulfonate lithium salt, 2-bromoethanesulfonate sodium salt, 2- chloro-ethane sulfonate sodium salt, 2-bromoethane-bis (fluorosulfonyl) imide lithium salt.
  • Such halogenated alkyl anion salts form alkyl anions tethered to the metal anode, i.e., M- alkyl-A ⁇ + M where M is the metallic anode electrode surface and A " + M is the anion salt.
  • Another aspect of the present disclosure is processes for preparing ionic membranes on metallic anode electrodes, which can be used in a rechargeable battery.
  • Such processes include electropolymerizing a polymerizable ionic liquid monomer onto the metal anode to form an ionic membrane thereon.
  • Other processes include adsorbing halogenated alkyl anion salts onto a surface of the metal anode electrode to form an ionic membrane thereon.
  • the IL monomer and the halogenated alkyl anion salts can be included with an electrolyte of the rechargeable battery. The addition of such ionomers in the electrolyte can help in the regeneration of the ionic membrane in repeated cycling of the battery.
  • the ionomer e.g., polymerizable ionic liquid monomer or halogenated alkyl anion salts or both, can be included as an additive in the electrolyte of a rechargeable battery at concentration of about 1% to about 30 % by weight such as of about 5% to about 20% by weight based on the total weight of the electrolyte.
  • the anodes protected with the ionic membrane of the present can be cycled stably with high Coulombic efficiency at high current densities.
  • metal anodes protected with ionic membranes of the present disclosure can exhibit coulombic efficiency exceeding 90% such as exceeding 95%.
  • Such protected anodes can exhibit stable cycling of over 100 cycles such as over 150 cycles.
  • Metal anodes that can benefit from the present disclosure include metal anodes that comprise substantially metallic lithium, metallic sodium, metallic aluminum, metallic zinc, etc.
  • Forming an ionic membrane on the surface of such anodes according to the present disclosure provides a solid electrolyte interface (SEI) that offers desirable (e.g., fast) ion transport between a bulk liquid electrolyte and a metal anode (e.g., Li or Na), or optionally an intercalating or conversion cathode, but at the same time protects the electrodes from physical contact with the liquid, which provides an important route towards creation of reactive metal anodes able to overcome chemical instability of the metal anode.
  • SEI solid electrolyte interface
  • an ionic membrane can be prepared as an SEI film formed directly on a metallic anode, e.g., a metallic sodium anode, through electropolymerization of a polymerizable ionic liquid monomer in a liquid electrolyte. It was found that such membranes markedly increase the stability of anodes to failure. We also found that unlike Li anodes, which can fail by any of the processes discussed in the Background section above, Na anodes almost always fail as result of electrolyte degradation.
  • the ionic membrane of the present disclosure advantageously can exhibit exceptional chemical and electrochemical stability in contact with reactive metals and in certain environments stabilize lithium and sodium metal anodes against dendrite formation such as with aprotic liquid electrolytes.
  • Theoretical work suggests that the tethered anions in an ionic liquid can improve the stability of Li plating during the battery recharge by acting as a supporting electrolyte. This has been verified by the experimental studies which show that dendrite free electrodeposition can be achieved by uniforming ion distribution by contacting lithium to functional glass fiber or solid polymer electrolyte.
  • An ionic liquid additive is believed to reduce the magnitude of destabilizing electric fields near the anode by providing a localized supply of anions able to support a high cation flux at the electrode.
  • Secondary sodium-ion and sodium-metal batteries offer multiple advantages over their lithium counterparts for portable storage in electric vehicles and locomotives as well as for stationary storage in power stations.
  • motivations for interest in these batteries include the low cost and high natural abundance of sodium, the high theoretical capacity (1166 mAh/g) and moderate redox potential (-2.71 V versus the standard hydrogen potential) of the sodium anode, and the fact that high-temperature sodium-sulfur (Na-S) and Na-metal chloride (Na/MeCl 2 ) batteries have already been demonstrated to be commercially viable technologies for grid storage and for electrification of transportation.
  • Room-temperature sodium batteries based on high-voltage intercalation cathodes or energetic conversion cathodes have already been reported to overcome some of these difficulties, however the focus on improvements afforded by ambient- temperature operation, typically gloss over fundamental challenges associated with long term stability of a sodium metal anode in liquid electrolytes.
  • Ionic membranes formed directly on metallic sodium anodes can mitigate the stability problems of such anodes.
  • the following provides an example of preparing such an ionic membrane from a polymerizable ionic liquid (IL) monomer.
  • Electrochemical polymerization of reactive monomers on metallic surfaces is a well-established method to fabricate functional polymer thin films for protecting metals and electronic devices, including sensors.
  • the approach offers several advantages over other polymerization techniques that may also be used to create coatings on metals, including: (i) it combine polymer synthesis with thin film formation; (ii) it eliminates the need for exogenous oxidants to initiate the polymerization; and (iii) properties of the membrane, including its thickness, morphology, and porosity are controlled by transport processes in the film itself.
  • Figure 1 is a schematic representation of the process, showing how it can be used to create an ionic polymer membrane on the surface of a metal anode, e.g., a sodium anode.
  • the polymerization reaction is believed to progress via the usual steps (initiation, propagation, and termination) that govern free radical polymerization processes. Initiation occurs during charging, wherein the unsaturated ionic liquid monomers accept electrons to form reactive radical species. These species react with monomers to increase the size of the radicals, propagating the polymerization process and creating a thin, porous membrane in conformal contact with the anode.
  • the molecular structure of the ionic liquid (IL) monomer was found to be a factor in regulating the structure and morphology of the polymer membrane as well as in controlling the degree of polymerization achieved. It was reported that polymerization of IL molecules may result in degradation of properties of the monomers, including ionic conductivity, due to elevation of the glass transition temperature and reduced number of mobile ions after covalent bonding of the component ions.
  • a constant current of 1 mA/cm 2 was applied to the cells to initiate polymerization until the voltage goes diverging with no current passing through the cell, at which point the electrodes are probably covered by the films and completely insulated.
  • the morphology of the polymer film was examined by scanning electron microscopy (SEM). Both DAIM and AVIM monomers are able to polymerized by charges with good adhesion and contact to the stainless steel electrode, while AMIM barely forms a film on the surface likely due to limited unsaturated components on the ionic liquid.
  • a uniform thin, membrane was found to cover the rough and scratched surface of the stainless steel electrode by polymerizing DAIM monomer.
  • the surface topography of the film formed by DAIM was further characterized by atomic force microscopy (AFM) in tapping mode.
  • a smooth and uniform height/topography image was seen from a DAIM prepared film on stainless steel, which was comparable with an SEM image.
  • a scratch was made to expose the stainless steel and allow measurement of the height from the stainless steel surface to the upper polymer, giving a thickness of about 80 nm.
  • M w molecular weight
  • PDI polydispersity index
  • AMIM forms oligomers (Mw of about 896 g/mol) (possibly due to the limited unsaturated double bonds), while DAIM and AVIM monomers were capable of forming large molecular weight polymer films (Mw of 58,540 g/mol and 122,100 g/mol, respectively) consistent with the film morphologies characterized by SEM.
  • SEM SEM
  • DAIM DAIM-like membranes
  • those based on AVIM have molecular weight about twice as large and less open morphologies.
  • DAIM was selected for further evaluation.
  • DAIM monomer was used as additives in liquid electrolytes to form ionic membranes in a variety of configurations on sodium metal anodes.
  • the Coulombic efficiency (CE) for sodium stripping and platting processes was determined from galvanostatic experiments in a Na/stainless steel cell. Initially, a predetermined amount of sodium (1 mAh/cm 2 ) was plated on the stainless steel electrode at a constant current of 1 mA/cm 2 . In the following cycle, a fraction (1/6) of the sodium was striped and plated from the stainless steel repeatedly at the same current density. Under these conditions, the CE can be calculated based on the simple formula proposed by Aurbach (/. Electrochem. Soc. 1989, 136, 3198- 3205).
  • the low CE is also consistent with previous reports in cycling experiments in carbonate electrolytes in which all of the plated sodium was stripped from the stainless steel electrode each cycle. Consistent with the discussion in the introduction, the authors explain the low CE for sodium metal anodes in terms of formation of non-uniform solid electrolyte interphase as well as dendritic growth.
  • electrolytes containing DAIM as an additive exhibit markedly improved Coulombic efficiency with values as high as 95.0 % measured at a current density of 1 mA/cm 2 .
  • cells containing DAIM exhibit vastly improved stability in long- term cycling measurements and lower overpotential compared with those containing MPIM. It is important here to note that while MPIM additives in carbonate electrolytes were reported previously to prevent dendrite formation in lithium metal batteries, the material only has a limited effect in improving the CE of the sodium metal anode, with only a 60 % CE being achieved. As the surface of the neat stainless steel electrode is relatively rough, this experiment tentatively confirms our previous finding that DAIM monomer helps form a uniform ion conducting polymeric membrane that not only protects the sodium metal surface, but facilitates transport at the anode.
  • the oxidation currents after the breakdown voltage are seen to be much lower for IL containing electrolytes than for the control electrolyte, indicating that the IL containing electrolytes have better electrochemical stability than the neat liquid electrolytes. It is also noted that small oxidization peaks were observed between 2 to 4 V for the electrolytes containing DAIM and AVIM, possibly indicative of an electron-transfer-induced polymerization process. The peak current increases linearly with the increase of the root mean square of the scan rate, indicating a diffusion-limited controlled polymerization process.
  • an in-situ optical microscopy technique was applied to directly visualize how sodium deposits in a quartz cuvette optical Na/Na symmetric cell.
  • a constant current of 1 mA/cm 2 was applied to polarize one electrode and we choose this current to make the study consistent with our previous test in coin cells.
  • Light microscopic images of the sodium electrode at different deposition times in a 1M EC/PC-NaC10 4 electrolyte were obtained. Due to the softness of sodium metal, the pristine sodium electrode surface was not perfectly smooth.
  • the electrode was gradually covered by two types of deposits-thin fiber-like and bulky mushroom-like, which were formed in a dynamically swinging movement manner. Both types of deposits grow not in a specific direction but spark randomly, which probably was due to the unevenness and defects of the electrode surface.
  • the shinning fiber-like deposit was discovered previously on sodium metal surface at a very low current density of 57 ⁇ /cm 2 and on lithium electrodeposition as well.
  • the bulky black sodium deposit was first discovered to the best of our knowledge, we tentatively attribute its formation to the uncontrolled side reaction with electrolyte.
  • the grows of the needle deposits may related to the effective pore size ( ⁇ 1 ⁇ ) of the polymer membrane, which was approximated from the storage modulus (4.05*10 " 3 Pa) of the polymeric DAIM.
  • the effective pore is in the similar length scale to that of the needles and much smaller than mushroom deposits, it can successfully block the growing pathway of the mushroom deposits while some of the needles may penetrate through the film and continue to grow.
  • Na 3 V2(P0 4 )3 is attractive because it exhibits high intercalation potential of around 3.4 V (vs Na + /Na), which makes Na 3 V2(P0 4 )3 a good candidate for next generation cathode materials for electrical energy storage, however, due to the larger ionic radius of sodium, it is a challenge to allow stable Na ion extraction and insertion.
  • Previous work usually applied fluoroethylene carbonate (FEC) as electrolyte additive to stabilize the passivation layer between electrode and electrolyte interphases, however FEC is known to decompose and forms hazardous HF gas during electrochemical process. Therefore, it is urgent to develop alternative methods to stabilized this type of cell.
  • FEC fluoroethylene carbonate
  • SPAN composite cathode was capable of delivering high capacity and cycle stability in lithium metal batteries, and it is compatible with carbonate electrolyte. For these reasons, Na 3 V2(P0 4 )3 and SPAN serve as good candidates for investigating the electrochemical stability of the protected sodium anode in rechargeable batteries.
  • Figure 3A reports the electrochemical characteristics of Na-Na 3 V 2 (P0 4 )3 cells based on the DAIM treated Na metal anodes.
  • a floating point test from 3 V to 5 V gives a time dependent current response for the cell with protected sodium electrode up to 4.8 V, while an irregular and noisy current response was observed for the control cell at almost entire voltage ranges.
  • the improved cell stability over different voltage ranges directly relates to the reduced side reaction between sodium anode and aprotic electrolyte. This enhanced cell stability also reduces the overpotential during galvanostatic cycling test, which results in higher cycling stability and coulombic efficiency (Figure 3A).
  • Electron and optical microscopy as well as electrochemical analysis indicate that IL monomer form a protective film on the Na anode and stabilize deposition of sodium by at least two mechanisms. First, they form an ionic polymeric SEI layer that protects sodium metal from parasitic side reactions with the liquid carbonate electrolyte. Second, they appear to utilize a previously reported tethered anion effect to stabilize deposition of Na. Our finding underscores the benefits of protecting sodium metal anode in the application of inexpensive rechargeable sodium metal batteries bearing high voltage or high specific capacity.
  • Another aspect of the present disclosure includes ionic membranes that form stable solid electrolyte interphases between a metal anode and electrolyte based on a halogenated alkyl anion salt, e.g., a bromide ionomer, which can adsorb onto the metal anode, e.g., a Li anode.
  • a halogenated alkyl anion salt e.g., a bromide ionomer
  • Such ionic membranes can advantageously exhibit three attributes required for stable anode operation such as L1-O 2 cell operation.
  • an ionic membrane is directly formed on a metallic anode such a metallic lithium anode for a rechargeable lithium-oxygen (L1-O 2 ) electrochemical cell.
  • a metallic anode such as metallic lithium anode for a rechargeable lithium-oxygen (L1-O 2 ) electrochemical cell.
  • Figure 4 illustrates such an embodiment.
  • the rechargeable lithium-oxygen (L1-O 2 ) electrochemical cell is peerless among energy storage technologies for its high theoretical specific energy (3500 Wh/kg), which far exceeds that of current state-of-the-art Li-ion battery technology.
  • L1-O 2 cells are under intense study for applications in electrified transportation because they are viewed as the gateway to Li-air storage technology that is capable of offering competitive specific storage capacities to fossil fuels.
  • a L1-O 2 cell includes a Li metal anode, an electrolyte that conducts Li + ions, and uses O 2 gas hosted in a porous carbon or metal support as the active material in the positive electrode (cathode).
  • the cell operates on the principle that L1 2 O 2 is reversibly formed and decomposed in the cathode, with the net electrochemical reaction of 2(Li + + e ⁇ ) + O 2 ⁇ L1 2 O 2 at an equilibrium potential of 2.96 V versus Li/Li + .
  • the ionic membrane can be directly formed on a metallic anode by including an ionomer such as a halogenated alkyl sulfonate salt together with a liquid electrolyte in the rechargeable battery.
  • an ionomer such as a halogenated alkyl sulfonate salt
  • a halogenated alkyl sulfonate salt can adsorb directly onto the anode surface forming a tethered alkyl anion that supplies ions near the anode electrode and stabilize the anode metal electrode.
  • the electrolyte ionomer salt additive (2- bromoethanesulfonate lithium salt) investigated for the present embodiment can react with lithium as provided in the scheme below.
  • the particular ionomer was chosen for this embodiment because of its ability to react with lithium to simultaneously anchor lithium ethanesulfonate at the anode/electrolyte interface and to generate partially soluble LiBr in the electrolyte.
  • the specific ionomer chemistry selected for the study is motivated by four fundamental considerations. First, recent continuum theoretical analysis and experiments indicate that tethering anions, such as sulfonates at the anode/electrolyte interface, lowers the potential at the interface during Li deposition and in so doing stabilizes the deposition.
  • JDFT joint density functional theoretical
  • the short hydrocarbon stem that connects the tethered sulfonate groups to Li should allow a dense hydrocarbon brush to form at the interface to protect the Li electrode from chemical attack by a high-DN electrolyte required for stability at the cathode.
  • soluble LiBr undergoes electrochemical oxidation and reduction in an appropriate potential window to function as a soluble redox mediator.
  • Cryo-focused ion beam (cryo-FIB) was used to characterize the morphology and thickness of the ionomer-enriched electrode/electrolyte interface with the liquid electrolyte intact but cryo-immobilized.
  • a symmetric lithium cell (with an ionomer-based electrolyte) was opened manually, and the sample was snap-frozen by immediately plunging it into slush nitrogen to preserve the electrolyte and to avoid air exposure.
  • the sample was then transferred under vacuum into an FEI Strata 400 FIB fitted with a Quorum PP3010T Cryo-FIB/SEM Preparation System and maintained at -165°C for the duration of the experiment.
  • XPS analysis was also performed using postmortem measurements on lithium anodes harvested from L1-O2 cells subjected to different running conditions.
  • High- resolution scans for anodes retrieved after cycling or after a single discharge with the ionomer additive in the 1 M L1NO 3 - N,N-dimethylacetamide (DMA) electrolyte were reviewed and compared to a corresponding Li anode without the ionomer. From this comparison, it is apparent that after the first discharge, a Li Is peak at 55.2 eV is observed on anodes with or without the ionomer present in the electrolyte. The peak may be attributed to the presence of LiOH, L12O2, and L12CO 3 .
  • Li Is peak is observed at 53.8 eV, accounting for about 85% of lithium, only in spectra of anodes cycled in the presence of the ionomer additive. This peak is indicative of the formation of a different SEI in electrolytes containing the ionomer; Li Is peaks with comparable binding energy are reported for organometallics containing Li-C bonds (54.2 eV). This observation is consistent with the ionomer reacting at the Li anode surface to form a lithium ethanesulfonate-rich SEI at the interface. Also, the fact that this binding energy is observed in the cycled anodes confirms that the SEI layer is stable and present even after repeated insertion and extraction of lithium ions into the underlying electrode.
  • the O ls peak at 532.2 eV comprises approximately 18% of the oxygen signal in cells without the ionomer additive, whether the anodes originate from cells that were subjected to a single discharge or were cycled.
  • the 532.2-eV peak has been previously reported to originate from sulfonates, which accounts for 27 and 38%, respectively, of the oxygen signal when the anode is discharged once or cycled in the presence of the ionomer additive.
  • the corresponding sulfur atomic contribution for the same materials can be computed from the wide survey scans to be about 2% for the once discharged anode and about twice as high for the cycled anodes.
  • the high-resolution scans of Br 3d reveal the formation of a single bond (a 3ds/2 and 3d 3 /2 doublet) with a Br 3ds/2 peak at 68.5 eV when the anode is discharged once in the presence of the ionomer.
  • We attribute this peak to the formation of the Br-Li bond, which has been previously reported to occur at binding energies between 68.8 and 69.5.
  • the same peak persists when the anode is cycled in the presence of the ionomer, but with a contribution of only around 15%.
  • the reduced Li-Br species in the anodes of cycled cells is an indication of LiBr being solvated by the DMA electrolyte that can further participate in the redox mediation of oxygen cathode recharging.
  • a more prominent Br 3d peak at 67.0 eV is observed only for the cycled anodes, likely originating from Br-C bonds [binding energies between 66.7 and 71.0 eV] in the SEI originating from an untethered ionomer.
  • the untethered ionomer in the electrolyte can help in the regeneration of the SEI layer in repeated cycling.
  • Our results based on XPS analysis thus show that the ionomer-added electrolyte forms a SEI layer of lithium ethanesulfonate and LiBr, in accordance with the proposed reaction mechanism.
  • the time-dependent interfacial impedance provides an even more sensitive indicator of the stability of the anode-electrolyte interphase in a high-DN solvent. It is seen that the initial interfacial resistances for control and ionomer SEI-stabilized Li electrodes are approximately equal (-50 ohms). However, there is an exponential rise in the interfacial resistance of the control cell over time consistent with rapid reaction between Li and DMA. It is important to note that this reaction is observed although L1NO 3 is present at large concentrations in the electrolyte. These results therefore challenge the view that L1NO 3 provides an effective means of passivating Li metal anodes against reactive liquid electrolytes.
  • Lithium-electrolyte stability The quality of lithium ion deposition on stainless steel substrates mediated by control and ionomer-containing 1 M L1NO 3 -DMA electrolytes were compared. For these experiments, cells were assembled with lithium as an anode and stainless steel as a virtual cathode. Lithium with a capacity of 10 mAh/cm 2 was deposited at a rate of 1 mA/cm 2 onto stainless steel, after which the cell was rested for a period of 10 hours and the voltage was monitored over time. For the cell including an ionic membrane, 10 wt% of 2-bromoethanesulfonate lithium salt was added to the electrolyte to form the membrane.
  • Figure 6 shows that in case of a control electrolyte, Li deposition takes place at a higher voltage compared to the ionomer-containing electrolyte. Also, it can be observed that after the rest period, the voltage measured in the control cells immediately rises to approximately 0.5 V. This high open-circuit potential after Li deposition is a reflection of the complete decomposition of Li deposits on stainless steel due to corrosion by the electrolyte. It is again worth noting that despite using the Li-pas sivating salt L1NO 3 at high concentrations in the electrolyte, the freshly deposited lithium reacts completely with the electrolyte solvent.
  • Figure 6 also reports the corresponding voltage profiles observed in rested cells containing the ionomer as an electrolyte additive. It is seen that the cell voltage remains close to 0 V (versus Li/Li + ), that is, near the open-circuit potential of a symmetric lithium cell, which means that the Li electrode is chemically stable in the reactive DMA electrolyte solvent.
  • the stability of the Li deposition reaction is normally assessed using three criteria: (i) magnitude of overpotential of lithium deposition, (ii) steep decrease of the cell voltage to zero with continuous charge- discharge, and (iii) a steady increase of the voltage over extended cycles of charge and discharge.
  • higher overpotential is indicative of formation of insulating products on the surface of the Li electrodes.
  • the voltage response for cells with ionomer-based SEI is low (approximately 6 mV), whereas the corresponding value for the control is much higher (approximately 150 mV).
  • the second criterion is related to the short-circuiting of the cell when dendritic lithium that formed at one or both electrodes bridges the two electrodes. It is apparent that this phenomenon is not observed either in the control or for the ionomer SEI-stabilized electrodes.
  • a rise in voltage over cycles represents an unstable SEI that grows continuously, eventually consuming the Li deposited on the stainless steel substrate. It was observed, after only two cycles at both current densities studied, the control cell fails after a steep rise in voltage. This is quite different from what is observed for cells in which Li is stabilized by an ionomer SEI, which is stable for over 150 cycles.
  • Figure 7 reports the number of cycles at which the cell voltage diverges as a function of current density (/).
  • the ionomer-based SEI is seen to improve cell lifetime at a fixed current density by nearly two orders of magnitude. These results underscore the effectiveness of the ionomer-based SEI in stabilizing electrodeposition of Li in amide-based electrolytes, which were previously thought to be unfeasible for lithium metal batteries because of their high reactivity with and ready decomposition by Li.
  • the LiBr created during the formation of the SEI should provide an even more powerful (than LiF) stabilizing effect on Li deposition.
  • the SEI created by the ionomer contains bound anionic groups in the form of lithium ethanesulfonate ( ⁇ - ⁇ 3 ⁇ 4 ⁇ 3 ⁇ 4-80 3 ⁇ ).
  • the electrolyte includes a combination of free and tethered anions.
  • researchers have realized the importance of single-ion-conducting electrolytes, because these electrolytes prevent the formation of ion concentration regions within a cell, leading to stable ion transport even at a high charge rate.
  • Complementary x-ray diffraction (XRD) analysis shows that the cathode product is exclusively L1 2 O 2 (no other products, such as LiOH, are observed).
  • the SEM analysis shows that L1 2 O 2 particles grow increasingly larger as the discharge progresses and nucleation sites for growth are filled, and the full discharge capacity of the cell is reached.
  • Analysis of the particle sizes on discharge reveals that, at low current densities (for example, 15 ⁇ /cm 2 ), large L1 2 O 2 particles (1 ⁇ and higher) are formed. Comparing these results to those reported by Lau and Archer (Nano Lett.
  • Redox mediation from lithium 2-bromoethanesulfonate is thought to aid in the electrochemical decomposition of the large, insulating L12O2 particles formed on the cathode. Support for this belief comes from the effectiveness of the recharge process as well as from the flat charge profile observed until the full capacity of the discharge is reached; the voltage ultimately begins to rise because of the set voltage limit of 4.3 V.
  • a L1-O2 cell with 1 M L1NO 3 -DMA in an ionomer-based SEI on Li can reach a high capacity through L1O2 disproportionation, fully use the formed L12O2 during the recharge, and cycles with features indicative of the presence of a redox mediator.
  • DMA with and without ionomers with a capacity cutoff of 3000 mAh/g and a current density of 0.04 niA/cm 2 were prepared. It was seen that both discharge and charge voltage curves tend to diverge to lower and higher values, respectively. Further, it was seen that the voltage profile becomes extremely noisy in the fifth cycle of the control electrolyte, whereas that with the ionomer additive is stable. This instability without ionomers can be attributed to the degradation of the electrolyte by reaction with the unprotected lithium metal.
  • One major benefit of cells cycled with ionomers is reduced overpotential during charge relative to that of the control cell, thus increasing cycling efficiency.
  • Lil In the absence of water in the electrolyte, Lil was reported to produce a gradual rise in the discharge voltage due to formation of iodine and similar products. LiBr was found to be ineffective in maintaining a steady charge voltage. In electrolytes with high water content and Lil, LiOH has been shown to be the primary discharge product, which has been reported to be thermodynamically impossible to undergo OER. Our results therefore clearly show that protecting the Li anode in a 1 M L1NO 3 -DMA electrolyte with a SEI based on bromide ionomer overcomes fundamental limitations of the anode, cathode, and electrolyte in previously studied systems and enables stable cycling of these cells.
  • the present disclosure demonstrates that the addition of an ionomer to an electrolyte, viz lithium 2-bromoethanesulfonate (ionomer) to 1 M L1NO 3 -DMA electrolytes, produces an ionic membrane that act like a SEI at the lithium surface that stabilizes the anode in L1-O 2 cells by at least two powerful processes.
  • an ionomer viz lithium 2-bromoethanesulfonate (ionomer)
  • 1 M L1NO 3 -DMA electrolytes produces an ionic membrane that act like a SEI at the lithium surface that stabilizes the anode in L1-O 2 cells by at least two powerful processes.
  • L1-O 2 cells based on lithium 2-bromoethanesulfonate exhibit flatter, more stable charge profiles and can withstand deeper cycling.
  • Electrochemical Characterization Protected sodium metal anode was created by charging Na/Na symmetric cell at constant current of lmA/cm2 for 10 hours in a carbonate electrolyte containing 20 wt% IL monomers.
  • Cell assembly was carried out in an argon-filled glove -box (MBraun Labmaster).
  • the room-temperature cycling characteristics of the cells were evaluated under galvanostatic conditions using Neware CT- 3008 battery testers and electrochemical processes in the cells were studied by cyclic voltammetry using a CHI600D potentiostat. Electrochemical impedance and floating tests were conducted by using a Solartron Cell Test System model 1470E potentiostat/galvanostat. For post-mortem studies, cells were disassembled in an argon-filled glove-box and the electrodes were harvested and rinsed thoroughly with the electrolyte solvent before analysis.
  • a cathode slurry was prepared by mixing 180 mg of
  • Electrolyte preparation L1NO 3 and LiTFSI were heated under vacuum overnight at 100°C to remove all traces of water and transferred directly into the glove box.
  • DMA Sigma-Aldrich
  • bis(2-methoxyethyl) ether diglyme; Sigma-Aldrich
  • solvents were dried over 3 A molecular sieves (Sigma-Aldrich).
  • Lithium 2-bromoethanesulfonate was obtained through ion exchange with sodium 2-bromoethanesulfonate (Sigma-Aldrich).
  • Cyclic voltammetry The cyclic voltammetry test was performed in a two- electrode setup of Lillair cathode. The batteries were cycled between 1.9 and 4.5 V at a scan rate of 1 mV/s several times.
  • Lillstainless steel cell The batteries were first swept to -0.2 V versus Li/Li + and then they were swept in reverse direction until the voltage diverges.
  • X-ray photoelectron spectroscopy X-ray photoelectron spectroscopy.
  • XPS was conducted using Surface Science Instruments SSX-100 with an operating pressure of ⁇ 2 x 10 ⁇ 9 torr.
  • Monochromatic Al K-a x-rays (1486.6 eV) with a beam diameter of 1 mm were used.
  • Photoelectrons were collected at an emission angle of 55°.
  • a hemispherical analyzer determined electron kinetic energy using a pass energy of 150 V for wide survey scans and 50 V for high-resolution scans.
  • Samples were ion-etched using 4-kV Ar ions, which were rastered over an area of 2.25 mm x 4 mm with a total ion beam current of 2 mA, to remove adventitious carbon.

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Abstract

L'invention concerne des batteries métalliques rechargeables ayant une couche de membrane ionique protectrice sur une anode métallique. La membrane ionique peut être formée à partir d'ionomères dans l'électrolyte, comprenant des monomères liquides ioniques polymérisables ou des sels anioniques d'alkyles halogénés. De telles membranes ioniques peuvent délivrer de manière continue des ions près de l'électrode anode et stabiliser l'électrode métallique anode.
PCT/US2017/067357 2016-12-19 2017-12-19 Couches protectrices pour batteries à électrodes métalliques Ceased WO2018118951A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020033963A1 (fr) * 2018-08-10 2020-02-13 Cornell University Batteries en aluminium aqueuses et leurs procédés de fabrication
WO2020185664A1 (fr) * 2019-03-08 2020-09-17 The Penn State Research Foundation Interphase polymère-solide inorganique-électrolyte destinée à des batteries métalliques stables dans des conditions d'électrolyte faible
WO2021247596A1 (fr) * 2020-05-30 2021-12-09 Cornell University Réseaux polymères réticulés fonctionnalisés, leurs procédés de fabrication et leurs utilisations
CN115394958A (zh) * 2021-05-24 2022-11-25 国家能源投资集团有限责任公司 锂金属负极及其制备方法以及锂金属电池

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037595A (zh) * 2018-07-16 2018-12-18 南京大学 锂负极保护层及其制备方法和应用
EP3813161B1 (fr) * 2019-10-22 2023-09-06 Samsung Electronics Co., Ltd. Batterie secondaire entièrement solide et procédé de fabrication de batterie secondaire entièrement solide
EP4059684A4 (fr) 2019-11-13 2023-12-06 Kurashiki Boseki Kabushiki Kaisha Feuille de fibres intégrée à une résine pour une formation sous vide, et corps formé et procédé de production de corps formé utilisant cette dernière
CN112271334B (zh) * 2020-10-26 2022-01-25 哈尔滨工业大学 一种以金属镁为负极材料的镁金属电池用负极成膜添加剂及其应用
US12009511B2 (en) 2022-02-18 2024-06-11 International Business Machines Corporation Method to protect a lithium metal anode in a rechargeable lithium metal battery
WO2024164026A1 (fr) * 2023-02-03 2024-08-08 Cornell University Anodes à charge rapide, leurs procédés de fabrication et leurs utilisations
CN115966680A (zh) * 2023-02-08 2023-04-14 烟台大学 一种镁改性钠金属负极材料及其制备方法和在钠金属电池中的应用
CN116093175B (zh) * 2023-03-21 2023-11-03 泉州师范学院 一种大面积图案化锡金属栅线电极的常温制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5686463A (en) * 1979-12-18 1981-07-14 Toshiba Battery Co Ltd Organic solvent battery
CN1114237C (zh) * 1996-02-16 2003-07-09 宇部兴产株式会社 非水二次电池
US6402795B1 (en) * 1998-02-18 2002-06-11 Polyplus Battery Company, Inc. Plating metal negative electrodes under protective coatings
DE60006150T2 (de) 1999-11-23 2004-07-22 Moltech Corp., Tucson Lithiumanoden für elektrochemische zellen
KR100477751B1 (ko) * 2002-11-16 2005-03-21 삼성에스디아이 주식회사 비수계 전해액 및 이를 채용한 리튬 전지
US7507502B2 (en) * 2003-03-28 2009-03-24 Hitachi Maxell, Ltd. Negative electrode having intermetallic compound that occludes/desorbs lithium as an active material layer on collector for non-aqueous secondary battery and non-aqueous secondary battery using the same
US7514180B2 (en) * 2004-03-16 2009-04-07 Toyota Motor Engineering & Manufacturing North America, Inc. Battery with molten salt electrolyte and protected lithium-based negative electrode material
US7255965B2 (en) * 2005-04-25 2007-08-14 Ferro Corporation Non-aqueous electrolytic solution
US8703333B2 (en) * 2009-02-27 2014-04-22 Toyota Motor Engineering & Manufacturing North America, Inc. Electrode compositions and processes
US20110104574A1 (en) * 2009-07-16 2011-05-05 Enerize Corporation Nonaqueous electrolyte for lithium Ion and lithium metal batteries
FR2950737B1 (fr) * 2009-09-30 2012-01-20 Electricite De France Compartiment negatif rigide pour batterie metal-air et procede de fabrication de celui-ci
WO2011074088A1 (fr) * 2009-12-16 2011-06-23 トヨタ自動車株式会社 Sel fondu à température ambiante, électrode, batterie, agent empêchant l'accumulation de charges et procédé d'observation d'un échantillon
JP2012033423A (ja) * 2010-08-02 2012-02-16 Sumitomo Electric Ind Ltd 金属多孔体およびその製造方法、それを用いた電池
CN103688400A (zh) * 2011-04-27 2014-03-26 联邦科学与工业研究组织 锂储能装置
JP2015520502A (ja) * 2012-06-19 2015-07-16 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 電解質添加剤とアイオノマー物品とを含む電気化学セル、ならびにその製造方法および使用方法
EP2969917B1 (fr) * 2012-09-12 2022-11-02 Drexel University Copolymères séquencés ioniques liquides polymérisés utilisés comme membranes de batterie
KR20140058177A (ko) * 2012-11-06 2014-05-14 한양대학교 산학협력단 리튬 설퍼 전지용 양극 활물질 및 이를 포함하는 리튬 설퍼 전지
US10573933B2 (en) * 2015-05-15 2020-02-25 Samsung Electronics Co., Ltd. Lithium metal battery
CN105280886B (zh) * 2015-09-16 2018-05-15 中国科学院化学研究所 金属锂负极表面原位处理方法与应用

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
CHEMSUSCHEM, vol. 9, 2016, pages 1600 - 1606
J. ELECTROCHEM. SOC., vol. 136, 1989, pages 3198 - 3205
JAKUB REITER ET AL: "-Allyl--methylpiperidinium bis(trifluoromethanesulfonyl)imideA film forming ionic liquid for graphite anode of Li-ion batteries", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 71, 10 March 2012 (2012-03-10), pages 22 - 26, XP028421960, ISSN: 0013-4686, [retrieved on 20120327], DOI: 10.1016/J.ELECTACTA.2012.03.088 *
JUNHUI ZHOU ET AL: "N-Allyl-N-Methyl Piperidinium Bis (trifluoromethanesulfonyl) Imide as a Co-Solvent in Li-Ion Batteries", ADVANCED MATERIALS RESEARCH, vol. 750-752, 30 August 2013 (2013-08-30), pages 1194 - 1198, XP055457322, DOI: 10.4028/www.scientific.net/AMR.750-752.1194 *
JUNYOUNG MUN ET AL: "Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries", SCIENTIFIC REPORTS, vol. 4, no. 1, 29 August 2014 (2014-08-29), XP055457324, DOI: 10.1038/srep05802 *
KAI ZHANG ET AL: "Recent Developments of the Lithium Metal Anode for Rechargeable Non-Aqueous Batteries", ADVANCED ENERGY MATERIALS, vol. 6, no. 20, 27 June 2016 (2016-06-27), DE, pages 1600811, XP055457013, ISSN: 1614-6832, DOI: 10.1002/aenm.201600811 *
M. D. TIKEKAR ET AL: "Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions", SCIENCE ADVANCES, vol. 2, no. 7, 15 July 2016 (2016-07-15), pages e1600320 - e1600320, XP055457015, DOI: 10.1126/sciadv.1600320 *
NANO LETT., vol. 15, 2015, pages 5995 - 6002
NAT COMMUN, vol. 7, 2016, pages 11722
SHUYA WEI ET AL: "Highly Stable Sodium Batteries Enabled by Functional Ionic Polymer Membranes", ADVANCED MATERIALS, vol. 29, no. 12, 23 January 2017 (2017-01-23), DE, pages 1605512, XP055456982, ISSN: 0935-9648, DOI: 10.1002/adma.201605512 *
ZHENGYUAN TU ET AL: "Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries", ACCOUNTS OF CHEMICAL RESEARCH., vol. 48, no. 11, 23 October 2015 (2015-10-23), US, pages 2947 - 2956, XP055457028, ISSN: 0001-4842, DOI: 10.1021/acs.accounts.5b00427 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020033963A1 (fr) * 2018-08-10 2020-02-13 Cornell University Batteries en aluminium aqueuses et leurs procédés de fabrication
US12015149B2 (en) 2018-08-10 2024-06-18 Cornell University Aqueous aluminum batteries and methods of making same
WO2020185664A1 (fr) * 2019-03-08 2020-09-17 The Penn State Research Foundation Interphase polymère-solide inorganique-électrolyte destinée à des batteries métalliques stables dans des conditions d'électrolyte faible
US12261298B2 (en) 2019-03-08 2025-03-25 The Penn State Research Foundation Polymer-inorganic solid-electrolyte interphase for stable metal batteries under lean electrolyte conditions
WO2021247596A1 (fr) * 2020-05-30 2021-12-09 Cornell University Réseaux polymères réticulés fonctionnalisés, leurs procédés de fabrication et leurs utilisations
CN115394958A (zh) * 2021-05-24 2022-11-25 国家能源投资集团有限责任公司 锂金属负极及其制备方法以及锂金属电池

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